08 Chapter1

Introduction
Chapter - 1
INTRODUCTION
1.1 Metallic corrosion

Contents 1.2 Polymeric coatings
1.3 Fillers (modifiers) for improving the corrosion
resistance of polymeric coatings
1.4 Polymer nanocomposite coatings
1.5 Mechanisms of corrosion protection by coating
1.6 Objectives and scope of the present work
A general introduction to polymeric coatings, nanofillers, polymeric

nanocomposites, their preparation and characterization is presented in this
chapter. The objectives and scope of the present work is also given in this
chapter.
Metals and alloys is still the most important engineering material and
hence corrosion of metals is one of the most challenging problems faced by
scientists and engineers for a long time. Corrosion control is a major
research area for the last 150 years. Preventing corrosion of metals by
protective surface coatings is a very broad topic. Improvement in aesthetic
appeal along with the protective function makes coatings most attractive in a
variety of applications such as buildings, automobiles, ships, aeroplanes,
domestic/business gadgets etc. The major fraction of surface coatings based
on metals is used for the protection of iron and steel because of its huge
volume of production. Most steel products are coated with other metals or
with polymeric coatings. Polymeric coatings are generally filled polymer
systems which have three principal components.
1 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

Chapter - 1
a) Polymeric binder which controls the drying characteristics of the

coating along with its physical and chemical properties.
b) Pigments which are finely ground insoluble fillers mixed with the
binding media.
c) Solvents which provide the required properties (eg: viscosity) for
applying the coating on the metal.
Recently nanoparticles have emerged as a very promising filler in
polymer systems because of their potential to impart attractive chemical,
biological and physical properties at very low concentrations. They have
made their inroads into coatings as well. Polymers modified with nanofillers
are often known as polymer nanocomposites. Two of the most active areas
of research in corrosion resistant coating technology are the use of
conductive polymer coatings and polymer nanocomposite coatings (1, 2).
Conductive polymer coating alone may be brittle and not an effective
barrier. The objective of this study is to combine the use of conductive
polymers and nanofillers in the form of conductive polymer based
nanofillers as modifiers for improving the corrosion resistance of epoxy
which is one of the most efficient polymeric coating material (3). In most
cases such fillers may make further addition of pigments unnecessary.
1.1 Metallic corrosion

Metals are thermodynamically unstable and undergo corrosion.
Economic loss resulting from metallic corrosion is huge. Fig 1 shows a
corroded refugee ship from China (a) and close up of the corrosion of the
ship showing general corrosion with additional localized corrosion below
the water line, attributable to the chlorides in sea water (b).
The most common type of corrosion can be considered as an

electrochemical process. General corrosion occurs at the surface of a metal
Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 2

Introduction
due to two half-cell reactions. In one of the half-cell reactions known as

anodic or metal oxidation reaction, electrons are produced. In the other half
cell reaction known as cathodic or reduction reaction electrons are
consumed. One is a reaction in which chemical species from the aqueous
environment remove electrons from the metal. The other is a reaction in
which metal surface atoms participate to make up for the electron
deficiency. The resulting exchange of electrons between these two reactions
produces an electric current at the metal surface. Measuring this electric
current is a commonly used technique to measure the intensity of corrosion.
Generally an electric voltage is supplied on the metal surface to balance the
supply and demand for electrons. The voltage imposed on the metal will
determine the nature of reactions (4).
Fig.1 Corroded Refugee ship from China. Courtesy: The Minerals,

Metals & Materials Society and ASM International 2011.
1.2 Polymeric coatings
The use of polymeric coatings is one of the most important

methods for minimizing corrosion. Polymeric coatings are essentially of a
pigment dispersed in a solution of a binding medium. The binding medium

Chapter - 1
or polymer will decide the basic physical and chemical properties of the
coating but these will be modified by the nature and proportion of pigments
present. The sole function of the volatile component is to control the
viscosity of the paint for ease of manufacture and for subsequent
application. It is not possible to forecast with any accuracy what
combination of properties a particular formulation will have and the
formulation of paints for a specific purpose remains very much a
technological art.
Alkyds, polyester-amides, polyester polyether-amides,

polyurethanes, polyols and epoxies are the commonly used polymers in
coatings. Epoxy resins due to their excellent chemical corrosion resistance,
outstanding adhesion properties and low shrinkage are widely used in
coating applications.
1.2.1 Epoxy resins
The epoxy resin belongs to the family of thermosetting polymers

and is characterized by many outstanding properties such as excellent
mechanical strength and stiffness, chemical and corrosion resistance,
durability, stability when exposed to different environmental conditions,
low shrinkage upon curing and excellent adhesion to different materials (5).
They are extensively applied in many diverse applications and industrial
uses such as adhesives and coatings, matrices to produce fibre reinforced
composites, electrical components and insulators (6). Due to their strong
adhesion to a wide range of surfaces and their good chemical resistance,
epoxy resins are frequently used as anti-corrosive and protective coatings
for metals. Along with the many outstanding properties of the epoxy resins,
they also display some weaknesses such as brittle nature like other
thermosetting polymers, low thermal/ electrical conductivity, high

Introduction
coefficient of thermal expansion etc which restrict their use in more

demanding applications.
Epoxy resins fall into two types based on their molecular structure
and applications and are known as glycidyl epoxy and non-glycidyl epoxy
(Fig 2). Glycidyl epoxies can be further classified into three types on the
basis of their structure: glycidyl ether, glycidyl ester and glycidyl amine (7).
Epoxy
Resin
Non-
Glycidyl
Glycidyl
Glycidyl Glycidyl Glycidyl

Aliphatic Cyclic
Ether Amine Ester
Fig.2 Types of Epoxy resins
Glycidyl ether epoxy resin is the most widely used type formed
from the condensation reaction between two mols of epichlorohydrin and
one mol of bisphenol-A or diglycidyl ether of bisphenol-A (DGEBA). These
resins are transparent and colourless and are available in a variety of grades
having different viscosities. The properties of the resin depend on the extent
of reaction. These resins are generally used in solution form for coating
applications. Increase in the epoxy functionality increases the cross link
density and forms a more rigid polymer. Hence multi functional epoxies
have a glass transition temperature higher than difunctional epoxies even if
they are cured with the same hardener.

Chapter - 1
Glycidyl ester epoxy resins are usually less viscous, highly

reactive, highly adhesive and have good processability. Glycidyl amine
resins can be formed by reacting epichlorohydrin with an amine. They have
excellent temperature resistance and hence they are used in aerospace
applications. They also have outstanding mechanical properties and high
glass transition temperatures. Non-glycidyl ether epoxies are of two types.
One is cyclic aliphatic resins which are closed in structure and the other
having linear structure on to which epoxide groups are attached.
1.2.2 Curing agents/ crosslinkers for epoxy resins
A significant variable governing the development of a successful

nanocomposite is its cross link density. Aliphatic amines are curing agents
capable of curing epoxy resin at ambient temperature. The active hydrogen
present in the primary amine reacts with an epoxy group to form secondary
amine which in turn reacts with epoxy group to form tertiary amine. The
tertiary amine is capable of polymerizing the epoxy group. The properties of
the amine cured epoxy are dependent upon the curing speed, amount of
hardener and the type of epoxy resin. Aromatic amines cure only slowly at
ambient temperature due to the steric hindrance by the aromatic ring.
Aliphatic amine cured epoxy has good bonding properties and excellent
resistance towards water and solvents.
Anhydrides are generally used as curing agents for the long pot life
they provide. They possess good mechanical, chemical and electrical
properties with less amount of heat generation.
Polyamide amines react with bisphenol-A type epoxy resin to cure

at or below ambient temperature with moderate heat generation. It cures
very slowly giving the advantage of a long pot life. Imidazoles are a type of

Introduction
anionic polymerizing/curing agent for epoxy resin characterized by a

relatively long pot life. Liquid polymercaptan is gaining attraction as a low
temperature curing agent.
1.3 Fillers (modifiers) for improving the corrosion resistance

of polymeric coatings
Fillers are solid particles used in polymeric coatings to improve

properties and/or lower costs. Several factors such as the following should
be considered in selecting fillers for coatings.
a) Properties of the coating

b) Ease of production
c) Storage stability
d) Application of the coating on the substrate.
1.3.1 Fillers (modifiers) which influence barrier properties
The permeability of a coating refers to the ability of small

molecules to diffuse through the coating. The coating used for improving
corrosion should not allow liquid or gaseous molecules to pass through it
easily. As most filler particles are non porous solids small molecules cannot
go through the filler particles, and hence they have to travel around the
particles. A coating having low permeability towards small molecules will
have good barrier properties. The shape of the particles also has a significant
role in controlling permeability because the shape affects the orientation of
the particles during film formation. For eg: platelet shaped filler particles
like talc or mica lower permeability. Fillers which can lower permeability
can also improve corrosion resistance by forming a barrier thus retarding
diffusion of molecules which cause corrosion such as oxygen, water, salt

Chapter - 1
and acids. Further, fillers having a high pH can also retard corrosion
because corrosion is faster in acidic environment.
1.3.2 Conducting polymers as modifiers for improving the corrosion

resistance
Conducting polymers such as polyaniline (PANI), polypyrrole and

polythyophene work as a strong oxidant to steel inducing a potential shift in
the noble direction and hence can prevent corrosion. The strongly oxidative
conducting polymer helps the steel to be protected. Application of
conducting polymer in corrosion protection was first reported by DeBerry
(8) in 1985. He reported that stainless steel covered by PANI could keep the
former protected for relatively long period in sulphuric acid solution.
Camalat et al reported that PANI coatings electrochemically deposited from
oxalic acid provided good protection to steel in acidic media (9). Polypyrole
and its derivatives have also been investigated for their ability to provide
corrosion protection (10). Lacaze et al showed that electrochemically
synthesized pyrole coatings were effective for the corrosion protection of
oxidisable metals such as iron, aluminium and zinc (11). For the corrosion
protection two mechanisms have been proposed. One is the physical barrier
effect and the other is anodic protection. In the former polymer coating
works as a barrier against the penetration of oxidants and aggressive anions.
In the latter the conducting polymer with strong oxidative property works as
an oxidant to the substrate. Toshiaki Ohtsuka (12) has given a good review
of corrosion protection of steels by conducting polymer coating.
Conducting polymers can be coated over other substrates for

achieving synergistic electrical properties. The various methods of
deposition include in situ polymerization, physical coating, multi-layering

Introduction
and printing. Such materials can be used for achieving more sustainable and
low cost conducting polymer based applications (13).
1.9.3 Nanofillers
The addition of a nanofiller to an epoxy coating can be a good

choice to improve the scratch resistance of the coating, thus improving the
durability and the performance of the coating. Nanofillers can be metals (eg:
gold, silver, platinum, zinc), semi-metal (eg: silica nanoparticles, layered
silicates) or non-metal (organic) (eg: carbon nanotubes, nanofibers,
graphene).
All types of fillers having atleast one dimension less than or equal to
100 nm can be considered as nanoparticles. Nanofillers are generally
classified as 0D nanoparticles (size in all dimensions below 100 nm) (eg:
spherical silica), 1D nanoparticles (one particle dimension exceeds 100 nm)
(eg: Carbon nanotube, Halloysite nanotube) and 2D nanoparticles (two
dimensions exceed 100 nm) (graphene sheets).
Nanomaterials are a very interesting development of recent times.

One of the main applications of nanomaterials is nanofillers for improving
the performance of polymers. Nanofillers can significantly improve or
adjust the properties of the polymers into which they are added such as
optical, electrical, mechanical, thermal, fire retardant etc at very low
concentrations. The small size of the nanoparticles enables them to penetrate
into ultrasmall holes in the polymer matrix thereby enhancing the strength
and durability of the coatings (14 - 17). Introducing nanofillers to coatings is
a very active research area. A wide range of nanoparticles such as ZnO (18),
Ag2O (19), ZrO2 (20), clay (21), SiO2 (22), Fe2O3 (23), MoS2 (24), Zeolite
(25), halloysite (26), CNT (27) and graphene (28, 29). Nanoparticles due to

Chapyter 1
their large specific surface area can significantly promote barrier properties
of coatings against the penetration of corrosion promoting species like
water, oxygen and chloride ions (30, 31).
1.9.3.1 Carbon based nanofillers
Carbon based nanomaterials (eg: carbon nanotubes, graphene

nanosheets) have attracted much attention due to their outstanding
properties (32). The carbon nanotube as 1D and graphene as 2D allotropes
of carbon nanostructures have unique electrical and thermal conductivity,
mechanical performance and optical properties (33). Improving the
corrosion protection performance of polymer coatings by adding carbon
based nanomaterials has a significant role (34). Epoxy nanocomposites
change from an insulator to conductor when a conductive filler is added (35,
36). A high electrical conductivity is promoted by an effective direct
electrical contact between the nanoparticles (35, 37) as shown in Fig 3.
Fig.3 Development of electrical conductivity

in nanocomposites (39).

Introduction
The presence of uniformly dispersed nanofillers is a basic

requirement for such conductivity (38). In addition a critical loading called
electrical perculation threshold is needed. The perculation threshold is
usually achieved using 0.5 to 1 wt % nanofiller (40, 41).
a) Carbon nanotubes
Carbon nanotubes (CNTs) were discovered by a Japanese physicist

Sumio Iijima in 1991 (42). CNTs are a very active research area in recent
times. CNTs are elongated fullerenes having either single or multiple rolled
up sheets of carbon atoms (graphene) making up the walls with capped ends
(43). Single walled carbon nanotubes (SWCNTs) and multi walled carbon
nanotubes (MWCNTs) are the common types of CNTs. SWCNTs have only
a single layer of graphene sheet located around a central hollow core while
MWCNTs are generally composed of more than one graphene shell
coaxially located along the tube. The diameters of the nanotubes are in the
range 1-10 nanometer (Fig 4).
Fig.4 Schematic diagram of multi-walled carbon nanotube

(MWCNT) (drawn using ChemDraw software)
Both SWCNTs and MWCNTs have exceptional mechanical,
thermal, chemical, magnetic, optical and electrical properties. With high
length to diameter ratio (generally more than 1000) the tensile strength of

Chapter - 1
CNTs is found to be 100 times that of steel with a very low density.
Therefore CNTs are well known as light weight high performance materials
suitable for a variety of applications. Carbon nanotubes are also elastic in
addition to being very strong.
Carbon nanotubes possess extraordinary heat and electrical

conductivity. Their electric properties can be manipulated by application of
external magnetic field, mechanical force etc. Carbon nanotubes can also
withstand high temperatures.
The conventional methods of preparing carbon nanotubes are arc

discharge, laser ablation and chemical vapour deposition. But there are other
methods of preparation of late. Carbon nanotubes can be modified
physically, chemically or jointly for better dispersion in organic matrices.
b) Graphene nanosheets
Graphene is pure carbon in the form of a very thin, nearly

transparent sheet, one atom thick (Fig 5).
Fig.5 Schematic diagram of graphene

(drawn using ChemDraw software)

Introduction
Graphene is the basic structure of graphite, carbon nanotubes and

fullerenes. It is remarkably strong for its very low weight (100 times
stronger than steel) and it conducts heat and electricity with great efficiency.
Graphene shows unique properties such as high surface area (≈ 2630
m2/gm), high aspect ratio, low density, ultra high mechanical strength and
Youngs modulus ( ≈ 1 Tpa). Graphene with the unique combination of
bonded carbon atom structures with its myriad and complex physical
properties is poised to have a big impact on the future of material science,
electronics and nanotechnology. The reported properties and applications of
this two-dimensional form of carbon structure have opened up new
opportunities for the future devices and systems (44, 45). The effect of
dispersed graphene on anticorrosion performance of epoxy coatings was
evaluated by Shuan et al (46). The composite coatings displayed outstanding
barrier properties against water molecule compared to the neat epoxy
coating.
1.3.3.2 Nanoclays
Due to their wide availability and low cost nanoclays have been
developed for various applications (47). Nanoclays are widely employed in
epoxy for different purposes (thermal resistance, flame retardancy,
corrosion resistance etc) (48). Nanoclays are nanoparticles of layered
mineral silicates that can form complex clay crystallites by stacking these
layers (49). Depending on the chemical composition and nanoparticle
morphology nanoclays are classified into several classes such as
montmorillonite, bentonite, kaolinite, hectorite and halloysite. Organically
modified nanoclays (organoclays) have both organic and inorganic features
and hence they can be advantageously used in polymer nanocomposites.

Chapter - 1
Plate like montmorillonite is the most commonly used nanoclay.

Montmorillonite consists of approximately 1 mm thick alumino silicate
layer substituted with metal cations and stacked in an approximately 10
micrometer sized multi-layer stacks. By proper modification of the surface
montmorillonite can be dispersed in a polymer matrix to form polymer clay
nanocomposites.
Halloysite nanoclay is a naturally occurring alumina silicate

nanotube having average dimensions of 15 nm X 100 nm (50) (Fig 6).
Fig.6 Schematic diagram of halloysite nanoclay

(drawn using ChemDraw software)
Due to the hollow tube structure halloysite nanoclay is used for

rheology modification (51). Halloysite nanoclays are readily disperced in
various polymers without the need for exfoliation. This is achieved because
there are less abundant hydroxyl groups on the nanoclay surfaces compared
to montmorillonites. Further, halloysite nanoclays being tubular in shape are
excellent nanocontainers for various chemical molecules (52). Thus they are
efficient fillers for improving the mechanical and thermal properties of
polymers.

Introduction
1.3.4 Zinc powder
Galvanizing to give sacrificial protection to steel is a very common

technique for corrosion prevention (53). Galvanizing is usually done by hot
dipping and its main use is for semi-finished fabricated steel products like
sheets and pipes as an alternative to electrodeposition. Zinc melts at 419.5
°C and dipping is usually carried out in the temperature range 430 to 470
°C. For some applications a zinc coating is used in addition to protection by
a polymeric coating. Alternatively zinc powder can be used as a filler in the
polymer coating.
1.3.5 Hybrid fillers
Hybrid fillers such as silica nanoparticles and multi walled carbon

nanotubes (MWCNT) are found to generate epoxy based hybrid composites
with exceptional properties due to the synergistic effect resulting from the
combination of different nanofillers and the interactions between them (54,
55). Similarly epoxy based nanocomposites containing MWCNTs decorated
with ferrites nanoparticles are known to display unique electrical/
electromagnetic properties (56).
1.4 Polymer nanocomposite coatings
Composites are well known engineering materials. There are

innumerable number of natural (eg: wood, bone) and commercial (eg:
concrete) composites. Polymer composites form an important class of
materials used in a variety of applications. However, the nature of the
conventional (micrometer scale) composites results in property limitations.
Hence nanocomposites came into the scene due to strict demands on current
advanced materials. Compared to micrometric fillers the nanoscale fillers
have much higher aspect ratios and due to these higher surface area to

Chapter - 1
volume ratios the interfacial volume in a nanocomposite coating is much

higher than that of a polymer microcomposite developed from the same
materials (57).
Nanocoating has one component in the nanoscale. Due to the very

fine sizes of the particles filling ultra small spaces and blocking the
corrosive elements from diffusing into the surface of the substrate will be
more efficient. In addition, the high density of the nanocoatings grain
boundaries provides better adhesion properties which will increase the
lifetime of the coating (58). Nanocoatings also provide superior mechanical
and electronic properties which make them stronger and harder (59).
Nanocoatings also possess properties such as self healing (60), self cleaning
(61) and high scratch and wear resistance (62).
Fig.7 Different types of composites arising from the interaction of

layered silicates and polymer. (I) Phase separated microcomposite, (II)
intercalated nanocomposite and (III) exfoliated nanocomposite. (63)

Introduction
A polymer nanocomposite is a solid material consisting of atleast

two separated phases. The continuous or major phase is a polymer while the
dispersed or discontinuous phase is a nanofiller. Depending upon the extent
of interaction between the polymer and the nanofiller the morphology of the
nanocomposite will be different and a properly exfoliated system will
produce the best results (Fig 7).
Nanocomposite can be produced both by complex and simple

processes. Since nanocomposites are composed of nanosized particles with
large surface area the particles interface becomes very important and defines
the final properties of the nanocomposites. Nanocomposites can be
produced by similar processes used for conventional polymer composites.
The size, shape and volume fraction of the nanoparticles are critical factors
in deciding the properties of the nanocomposite.
Polymer nanocomposite coatings are developed by the

incorporation of nanoparticles into the polymer coating significantly
improving the mechanical properties of the coating (64, 65). Epoxy coating
modified with titanium dioxide nanoparticles showed good improvement in
impact strength. The improvement may be due to two mechanisms.
a) The nanoparticles occupy pinholes and voids in the thin film coating
thereby reinforcing the matrix through a reduction of total free volume
and enhancement of crosslink density. This means that the cured
nanocomposite coating has reduced chain segmental motions and
improved stiffness.
b) Nanoparticles may prevent epoxy disaggregation.
Nano SiO2 in epoxy coating increased Young’s modulus up to 20

times (66).

Chapter - 1
Incorporation of nanofillers into polymer coatings can enhance

thermal stability by acting as a superior insulator and a barrier to mass
transport of volatile products generated during decomposition (67). Adding
nanofillers into the polymer coating modifies its glass transition
temperature. An increase in Tg has been reported in several cases (68-70).
In the case of epoxy based coatings metal oxide nanoparticles

markedly improved the corrosion resistance of coated steel (71). The
performance of Halloysite clay is very significant in this case. Incorporation
of nanosilica into epoxy reduced its friction and wear at low concentrations.
Layered silicates dispersed as reinforcing phase in a polymer coating is one
of the most important nanocomposites (72-74).
1.4.1 Synthesis of polymer nanocomposite coatings
Developing successful polymer nanocomposite coatings has two

challenges.
a) Chemical compatibility between the polymer matrix and the nanofiller

at the nanoscale
b) Homogenous dispersion of the nanofiller in the polymer matrix.
The interfacial interaction between nanofiller and polymer matrix

and the quality of nanofiller dispersion will significantly affect the quality of
the polymer/ nanofiller composite (75). These two critical features
determine the polymer nanofiller composite morphology and its bulk
properties such as strength, modulus, thermal stability etc (76). Improving
the compatibility between the nanofiller and the polymer matrix may help to
get a homogeneous dispersion of the nanoparticles in the polymer matrix. In
most cases the van der Walls attraction between nanoparticles promotes
formation of clusters and agglomerates. In addition hydrophilic

Introduction
nanoparticles and hydrophobic polymers are not compatible which result in

poor interfacial adhesion resulting in poor dispersion and properties. To
overcome these interfacial problems a variety of synthesis routes have been
developed to control the chemistry and morphology.
There are three major synthesis procedures for developing polymer/

nanofiller composites: melt blending, solution blending and in situ
polymerization (77). The solution blending technique often yields better
dispersion of the nanofillers in the polymer matrix in comparison with melt
blending due to its low viscosity and high agitation. But melt blending is
more economical and eco-friendly (78). The in situ polymerization method
is more versatile and also likely to provide uniform dispersion (79).
1.4.1.1 Solution blending
Solution blending is done using a solvent to suspend the nanofiller.

In the case of layered nanofillers this may cause swelling at the layers and
help exfoliation of the filler (80). When it is mixed with the polymer the
polymer chains may intercalate and displace the solvent within the
interlayer of the filler (81). Upon solvent removal (eg: by vaporization) the
intercalated sheets reassemble resulting in polymer nanofiller composite.
The dispersion of the nanofiller requires strong agitation. Of late,
ultrasonication is employed to improve the dispersion of the nanofiller.
Even though solution blending produces relatively uniform nanofiller
dispersion the method uses large amounts of organic solvents. Hence melt
blending is preferred on an industrial scale.
1.4.1.2 Melt blending
In this method the desired amount of nanofiller is mixed with the

polymer at a temperature above the softening point of the polymer. The

Chapter - 1
absence of solvents make the process more economical and environment

friendly. In the case of thermoplastics the blending can be done along with
processing methods such as extrusion and injection moulding. Melt mixing
can be done as a batch process (eg: in an internal mixer) or as a continuous
process (eg: in an extruder) (82). The mixing parameters are residence time,
shear, temperature and pressure. Layered nanofillers can be well exfoliated
and dispersed into the polymer matrix. The melt blending method often
leads to insufficient filler dispersion which causes aggregation particularly
at high filler contents (83). Hence in situ polymerization is often more
effective.
1.4.1.3 In situ polymerization
In situ polymerization can be done in different ways.
a. In situ polymerization in the presence of the nanoparticles or in situ

synthesis of nanoparticles in the presence of the polymer.
b. Nanoparticles and polymer are both formed in situ.
The in situ polymerization technique is likely to develop

intercalated and/or exfoliated structures which result in improved thermal
stability and mechanical properties in the case of layered fillers (84).
Ultrasonication can be done along with in situ polymerization to improve
the quality of the nanocomposite (85).
1.4.1.4 Ultrasonication
Utrasonication is widely used for proper dispersion of the

nanofillers. Ultrasonication transfers high amounts of energy disrupting
physical and chemical interactions. Therefore it has been widely used for
dispersing, emulsifying, crushing and activating particles (86). Further,
ultrasound energy is able to break C-C bonds leading to the formation of

Introduction
radicals. These radicals can bond to the nanofiller surface in nanocomposite

systems (87) and enhance the polymer-filler interaction. Several studies are
available on the efficiency of ultrasonication in nanocomposite preparation
(86 - 89). High power ultrasound has been successfully used to break up
silica agglomerates in ethylene propylene diene monomer rubber (EPDM)
(89).
1.4.1.5 Depositing polymer nanocomposite coatings over metal

substrates.
Nanocomposite coatings can be deposited on metal substrates by

mechanical, physical or chemical methods (90). Mechanical deposition is
the most straightforward method and can be done through spray, paint, spin
coating or dip coating. Physical deposition can be done by either bonding,
condensation or sputtering. Chemical deposition can be done through
plating, sol-gel etc. Each of the techniques of thin film deposition on the
surface of the substrate affect the uniformity and surface properties such as
strength, fracture toughness and ductility (91).
1.4.2 Characterization of polymer nanocomposite coatings.
The incorporation of nanoparticles in epoxy resins allows

modification of many properties such as improved corrosion resistance,
improvedmechanical properties, improved thermal and electrical
conductivity, improved electric permittivity and low dielectric loss, reduced
flammability etc. compared to the neat polymer.
In the present study nanocomposite coatings are proposed to be

developed to improve the corrosion resistance of substrates. So
characterization will be done based on the corrosion resistance and other
properties relevant to that.

Chapter - 1
1.4.2.1 Corrosion resistance
The major reasons for the high corrosion resistance of epoxy

nanocomposite coatings are the crosslink density of the matrix and its
barrier properties. However when the coating is exposed to the corrosive
environment for a long time it can develop holes and defects permitting easy
flow of corrosive species (92). Addition of layered nanofillers can create
tortuous pathways for the flow of corrosive agents compared to neat epoxy
coating improving the corrosion resistance (93). Epoxy coatings have
excellent chemical resistance and have strong adhesion to substrates.
However they are brittle in nature and have poor resistance to initiation and
propagation of cracks (94). Addition of nanofillers can prevent or delay the
formation of cracks by reducing the brittle nature of epoxy.
Polymer nanocomposite coatings can reduce corrosion in several

ways: by creating a more efficient protective barrier compared to the neat
polymer, by improving the electrical conductivity of the film etc. In addition
oxygen reduction on the surface of the polymer can reduce corrosion
reaction on the metal surface as shown in Fig 8.
Fig. 8 Corrosion prevention by creating an oxygen

deficiency on the metal surface (95).

Introduction
Electrochemical impedance spectroscopy (EIS) is widely used to

study corrosion resistance. EIS is an electrochemical technique that uses 3
electrodes: working electrode, a reference electrode and a counter electrode.
The instrument can measure the impedance for a wide range of frequencies
when an AC voltage with certain amplitude is passed in the circuit. The
measurements are taken as a function of immersion time. Resistance directly
indicates the corrosion resistance while capacitance indicates the water
uptake of the coating. Huttenen et al conducted EIS studies on epoxy
coating containing 1 and 3 wt % nanoclay. Resistivity was maximum and
dielectric constant was minimum for 1 wt % nanoclay which indicates that
there is an optimum concentration of nanoclay which gives best corrosion
resistance and least water uptake (96). Tomic et al tested epoxy clay
nanocomposite coatings with 1, 3 and 5 wt % nanoclay and observed that
the epoxy coating containing 1 wt % nanoclay provides the best corrosion
resistance. This result also shows that there is an optimum concentration of
nanoclay which provides the maximum corrosion resistance and corrosion
resistance decreases above this optimum concentration. This is probably due
to increased clay agglomeration above the observed optimum concentration
(97).
1.4.2.2 Barrier properties
One important factor which affect the corrosion resistance of the

coating is its barrier properties. In general the permeability of moisture or
oxygen through polymers depends on various factors such as
a) Structural characteristics and polarity of the polymer chains

b) Intermolecular interactions such as hydrogen bonding
c) Molecular weight and polydispersity
d) Degree of crosslinking or branching

Chapter - 1
e) Method of synthesis
f) Crystallinity
Polymer nanocomposites have very good barrier properties (98).

Polymeric nanocomposites containing Nanofillers such as clays or
graphene, carbon nanotubes, chitosan etc develop good barrier properties
(99 - 101).
A dispersion of nanofillers in the polymer matrix affects the barrier

properties of the coating in two ways.
a) By creation of a tortuous path for the diffusion of water vapour,

oxygen etc (93, 102).
Due to the impermeable nature of the nanofillers the molecules of
the gas must diffuse around them instead of taking a straight path
perpendicular to the surface of the coating. Hence the mean path for the
diffusion of the gas through the film becomes longer (103) (Fig 9).
Fig. 9 Tortuous path created by incorporation of clay

nanoplatelets in a polymer coating (adapted from 103)

Introduction
As shown in the Fig 6 in a coating composed only of polymer (I)

diffusing gas molecules take a pathway that is perpendicular to the coating.
But in a nanocomposite coating (II) diffusing molecules diffuse around the
impenetrable particles/platelets. This shows that the shape of the
nanomaterials has got a significant effect in promoting barrier properties.
Layered nanomaterials are the most efficient in promoting barrier
properties. Besides nanofiller content and aspect ratio the state of exfoliation
significantly affects barrier properties of nanocoatings (104).
b) By interaction between nanomaterials and the polymer.
If there are strong interaction between the nanofiller and the

polymer the polymer chains which are close to the nanomaterials can be
partially immobilized. Hence the movement of the gas molecules migrating
through such interfacial areas have restricted movement (105).
Fig.10 Water absorption curves of neat and filled epoxy coating epoxy
coating filled with unmodified and modified silicon nitride (106).

Chapter - 1
Resistance to liquid and gas permeation is very important for the

performance and corrosion protection of coatings. Fig 10 shows the water
absorption curves of neat epoxy coating and
All the three coatings show a similar behaviour showing two

stages. Water absorption increases quickly initially and then reaches a
saturation state. For the modified silicon nitride coating water absorption
progresses at the lowest rate and reaches saturation in 408 hr immersion in a
3.5% NaCl solution. Also the modified silicon nitride coating absorbs the
least amount of water among the three coatings at saturation. Naturally the
modified silicon nitride coating will provide a superior barrier to permeation
of the solution.
1.4.2.3 Mechanical properties
Nanocomposites have much improved mechanical properties such as

stiffness, strength etc in comparison to microcomposites (107 - 109).
Properly dispersed and aligned clay platelets can significantly improve the
stiffness of the polymer matrix. Fig 11 compares the modulus of an injection
moulded composite based on nylon 6 filled with organoclay (MMT
platelets) (nano) and glass fibers (micro).
The modulus of the nanocomposite is double that of the

microcomposite with more than three times the mass of glass fibers than
that of MMT platelets. Further, if the platelets are aligned in the plane of the
sample the same reinforcement will be observed in all directions within the
plane whereas fibers reinforce only along a single axis in the direction of
their alignment (109). In addition the surface finish of the nanocomposite is
much better than that of the microcomposite due to the nanometer size of
the clay platelets. Several properties of the nanocomposites are influenced

Introduction
by the size and geometry of the nanoparticles, eg: the Young’s and shear
moduli (110 - 116), the thermal expansion coefficient etc (110, 112, 117).
The interface is very crucial and hence the development of the mechanical
properties is dependent upon proper interfacial adhesion (110, 111, 113,
114).
Fig.11 Modulus of MMT filled versus glass fiber filled

Nylon 6 composite relative to matrix (107).
1.4.2.4 Characterization of the nanocomposite structure.
Reliable characterization techniques are required to resolve

nanosized scale features or the nano effect. This involves characterizing the
dispersion of nanofiller in the polymer matrix as well as to analyse the size
and shape of the nanofillers (118, 119). Generally lower concentrations of
nanofiller give exfoliated structure. TEM analysis of 1 wt % halloysite
nanoclay gives exfoliated structure with little agglomeration (65). WAXD
analysis showed that coatings with 1 and 3 wt % nanoclay develop
exfoliated structure while higher nanoclay results in agglomeration (118).

Chapter - 1
XRD and TEM analysis used to compare the effects of solution and melting
methods of dispersing nanoclay showed that the solution method provides
more exfoliation (67, 93).
a) Electron Microscopy
Scanning electron microscopy (SEM)
SEM is one of the most widely used techniques to study material

structure and surface characteristics. These microscopes have a resolution
between 1 and 5 nm. In addition to the high resolution they can also
penetrate to a fairly good depth. The principle of SEM is that an electron
gun generates electrons and accelerates them through lenses which focus the
beam with very small spot size. These electrons interact with the specimen
to a depth of about 1 micron and generate signals to form the image. Due to
the fact that magnifications from approximately 10 times to 500,000 times
are possible large scale images of nanometer size formations are well
detectable (120).
SEM can be used to determine the size and distribution of particles

by observing the fracture surfaces of the samples used for tensile testing.
Transmission electron microscopy (TEM)
The principle of TEM is that high energy electrons are transmitted

through an ultrathin section of the specimen. The image is formed due to
electrons scattering when the beam hits the specimen. The electrons are
emitted from an electron gun (filament). There are two or more condenser
lenses which control the diameter of the beam as it hits the specimen. TEM
analysis is widely used for the characterization of polymer nanocomposite
coatings particularly for the analysis of 2D layered nanofillers (120).

Introduction
b) Small and wide angle X-ray diffraction.
While wide angle X-ray diffraction (WAXS) gives information

about the molecular structure within crystalline domains, small angle X-ray
diffraction (SAXS) extends the scope to the characterization of nano
domains. Hence a combination of the two techniques represents a powerful
tool for the characterization of multi component polymer systems such as
polymer nanocomposites. WAXS is one of the most rapidly growing
techniques in polymer nanocomposite characterization because of the fact
that the structure of polymers and fillers at nanometer scale exhibits extreme
variability particularly in hybrid organic/inorganic composites with in situ
formed nanoparticles (120). While SAXS permits the determination of the
overall structure and dimensions on a length scale ranging from a few
nanometers to a 100 nm WAXS permits the investigation of molecular
packing in the sub nanometer scale. Typically for 2 theta >1° the diffraction
experiment is referred to as WAXS, for 1° > 2 theta > 0.3° as medium angle
X-ray scattering (MAXS) and for 2 theta < 0.3° as SAXS. In the case of
nanocomposites based on thermoplastic poly (butylene terephthalate) and
single walled carbon nanotube (SWCNT) the WAXS region corresponds to
the diffraction of the α crystalline phase of PBT, while the SAXS region
corresponds to the diffractions of the laminar crystals separated by
amorphous layers (121).
c) Thermal analysis
Differential scanning calorimetry (DSC)

Differential scanning calorimetry has been widely used in
analysing nanocomposites with respect to glass transition, melting,
crystallization and curing (122). In the case of layered nanofillers the
polymer chains are confined within the galleries restricting the segmental

Chapter - 1
motion of the polymer chains resulting in an enhancement of the Tg. This

effect can be easily analysed by the DSC. The increase in the glass
transition temperature can occur as a result of the interaction between the
polymer chains and the nanofiller surface (123).
Thermogravimetric analysis (TGA)
Thermogravimetric analysis conducted on several polymer

nanocomposites showed that many polymers filled with nanofillers such as
montmorillonite and carbon nanotube exhibited improved thermal stability
(ie a higher temperature for the onset of thermal degradation) (124 - 128).
When inorganic nanofillers are added to polymers the inorganic phase acts
as a superior insulator and mass transport barrier to the volatile products
generated during decomposition (67).
d) Fourier transform infrared spectroscopy (FTIR)
Fourier transform infrared spectroscopy (FTIR) can be used to

analyse the bonding between the polymer matrix and nanoparticles. FTIR
measures the absorption of infrared radiation by the sample material with
respect to the wavelength of the radiation. Using the absorption data
molecular components and structures can be identified. The signal detected
is analysed using Fourier transforms to provide infrared absorption spectra
usually presented as plots of intensity versus wave number. Infrared
wavelengths absorbed by a material identify as molecular structure. The
absorption spectrum is most often compared against a spectrum from a
known material for identification. Absorption bands in the range of 4000 to
1500 cm1 are typically due to functional groups. The range from 1500 to
400 is referred to as the fingerprint region and generally caused by
intramolecular phenomena very specific to each material (129).

Introduction
1.5 Mechanisms of corrosion protection by coating
The application of organic coatings on metal is the oldest means of

corrosion control and dates back to antiquity. Surface coatings can only stop
the corrosion process for a limited time. However, the selection of a suitable
paint can reduce the corrosion reaction to a rate that the structural integrity
of the steel can be maintained for the lifetime of the structure. Three main
methods of using coatings to control the corrosion of ferrous substrate are
barrier, cathodic and inhibitive protection.
Barrier protection provides high resistance to the diffusion of

water, ions and oxygen through the paint film to the substrate. It has also
been reported that barrier coatings can act as ionic filters (130) which means
that although water appears to readily permeate most paint films, the same is
not true of ions. Any water that does penetrate the coating is relatively ion-
free and hence has a high resistance, which inhibits the corrosion process at
the paint/ substrate interface. Therefore barrier coatings should be
formulated to resist the transmission of ionic species as well as oxygen
permeation. Whether protecting by resistance inhibition or oxygen
deprivation (Fig 12), the fundamental requirements of the barrier system are
that the coating should be impermeable to ionic moieties and if possible to
oxygen and that it should maintain adhesion to the metal under wet service
conditions.
Impermeability to ionic solutions and oxygen are entirely more

practical objectives, however, these factors are thought to be rate
determining for corrosion beneath barrier films. Permeability of the film to
water is generally thought to have greater direct consequence on deadhesion
leading subsequently to corrosion. It has been noted that corrosion beneath
barrier film can begin only after deadhesion has taken place and that if

Chapter - 1
adhesion can be maintained under wet service conditions then protection is

assured (131).
Fig. 12 Corrosion protection by Barrier coating
Cathodic protection is usually achieved by pigmenting the coating

with zinc dust which act as a sacrificial anode in contact with the steel
substrate as the cathode. Loading of the anodic zinc dust pigment must be
high enough to ensure a continuous current flow through the film itself and
across the interface (132) and as long as the conductivity of the metal is
sufficient to just sustain current flow from the film to the environment, the
steel remains protected (Fig 13).
Two fundamentally different classes of zinc rich primer have been

developed, the organic zinc rich primer and inorganic zinc-rich primer.
Organic zinc rich primers are based on a variety of resin systems including
epoxy/polyamide, moisture cured urethanes, high styrene resins, chlorinated
rubbers and epoxy esters. Control of the volumetric ratio of conductive
pigment to dry nonconductive binder ensures that the binder sheath around
each particle of pigment (zinc) does not become so thick that the current

Introduction
transfer is too greatly reduced or so depleted that cohesion and film strength
are lost (133).
Fig. 13 Corrosion protection by sacrificial coating
Inorganic zinc rich primers are fundamentally different to the

organic. Instead of employing a binder which encapsulates the zinc, these
materials employ a reactive binder, usually an inorganic silicates (either an
alkaline silicate or ethyl silicate) (134). Reactions involve loss of solvent or
water and hydrolysis of the silicate to the reactive acid (silicic acid) which
then undergoes self-condensation and chemically react with zinc atoms on
the zinc dust surface, forming a primary valance bonded matrix of
tetrahedral linked (poly) silicone oxide bridges between adjacent particles of
zinc (Fig 13). The resultant film matrix is entirely inorganic, open and much
more porous than the organic zinc film. As long as sufficient zinc remains to
act as an anode, even in the presence of chloride solution, the primer will
retain its ability to protect steel at least in the short term. Inorganic zinc rich
films are harder, stronger and for more adherent than are the organic zinc
rich films. The performance levels realized from the inorganics are superior
to those realized from the organic. In both organic and inorganic zinc rich

Chapter - 1
primers, the duration of cathodic activity is finite and the effect of zinc
polarization and the generation of zinc corrosion product gradually coverts
protection from the galvanic mechanism to a barrier mechanism (135).
The interval of galvanic protection before conversion to the

secondary protecting mechanism depends on the type and composition of
system and nature of the environment. In epoxy zinc rich primers, the
cathodic protection phase is briefer.
Inhibitive protection works by pigmenting coatings with specific

compounds such as anticorrosive pigments which chemically change the
environment at the primer/substrate interface (Fig 14). Inhibitive primers
control corrosion by modifying the interfacial (primer/metal) environment
so that passivation of the substrate metal may be achieved and maintained
(136).
Fig. 14 Corrosion protection by Inhibitive coating

Introduction
1.6 Objectives and scope of the present work
In general, coatings reduce corrosion by providing passive or active

protection. Passive protection is obtained when the coating forms a physical
barrier between the substrate and the surrounding environment. Active
protection is obtained when chemicals (inhibitors) prevent or minimize
corrosion. Polymer based nanocoatings can provide both passive and active
protection to the substrate.
In the performance of nanocomposites the part played by the

interface is very critical due to the attraction between the particle and the
matrix. As the size of the particle decreases to a nanometer scale the ratio of
surface area to volume increases drastically making the contribution of the
interface very critical. The interface characteristics become dominant in the
nanoscale world and this effect is called particle size effect (137, 138).
Inthermoset polymers the interaction between polymers is also important
due to the crosslinks formed between the chains. In highly crosslinked
structures the interaction between polymers is enhanced due to the high
crosslink density resulting in the limited mobility and increased stiffness
(139, 140). In this study it is proposed to investigate the effect of crosslink
density on the performance of the nanocomposite coatings by using two
types of crosslinkers for a selected epoxy resin so as to develop a soft
product and a hard product.
While protective conducting polymer coatings have been widely

used for metal corrosion control the use of polymeric coatings modified by
conducting polymers is meagre. Hence it is proposed to investigate the
modification of epoxy coatings by conducting polymers as the major thrust
of this study. Polyaniline (PANI) is one of the conducting polymers widely
being explored as a promising material for protection of metals against

Chapter - 1
corrosion because of its ease of synthesis, tunable properties and low cost
(141-145). Inspite of excellent electrical conductivity and outstanding
thermal stability polyaniline exhibits poor mechanical properties. So
application of PANI alone as a coating or as a corrosion resistant filler in
other conventional coatings is not very sound (146-148). Hence it is
proposed to coat PANI over an inert organic material chitin and an
inorganic material silica and to use PANI coated chitin and PANI coated
silica as potential modifiers in epoxy coating.
Chitin is a biopolymer derived from living beings and one of the

most abundant organic materials, being second only to cellulose in the
amount produced annually by biosynthesis. It occurs in animals, particularly
in crustacea, molluscs and insects where it is an important constituent of the
exoskeleton, and in certain fungi where it is the principal fibrillar polymer in
the cell wall. The problem associated with synthetic polymers such as
toxicity and non-biodegradability is suppressed by the use of biopolymers.
The important characteristic of biopolymers is its ability to degrade by
natural enzymes with their immunogenic behaviour. Chitosan is the
deacetylated derivative of chitin. Chitin and chitosan are inexpensive and
non hazardous. They possess various natural biological activities and have a
considerable potential to be utilized in a number of industrial applications.
Chitin nanowhiskers occur in biological tissues, according to structural
hierarchies, jointly with proteins and inorganic compounds (149).
Chemically chitin is identical to cellulose but the secondary hydroxyl group
on the alpha carbon atom of the cellulose molecule is substituted with an
acetamide group. The removal of the acetyl group in the alpha carbon atom
forms chitosan (Fig 15).

Introduction
Fig.15 Chemical structure of cellulose, chitin and chitosan
Unlike cellulose whiskers which are prepared by strong sulphuric

acid chitin whiskers are produced using hydrochloric acid (150-152). Chitin
whiskers are widely used for preparing polymer based nanocomposites
(153).
Silicon dioxide nanoparticles, also known as silica nanoparticles or

nano-silica, are the basis for a great deal of industrial research due to their
stability, low toxicity and ability to be functionalized with a range of
molecules and polymers. Silica nanoparticles are able to improve the
functional properties of the coatings for metals such as abrasion and scratch
resistance especially when their surfaces are properly modified (154). The
inclusion of silica nanoparticles in epoxy based coating is capable of
improving the corrosion resistance of metal surfaces (155). Among the
nanomaterials, nanosilica is generally applied in the preparation of

Chapter - 1
polymeric nanocomposites due to the high reaction between silica material

and the polymer matrix which resulted in higher dispersion ability of
nanosilica in the polymer (156,157). Further silica is widely used in
corrosion resistant coatings based on epoxy (158).
It is also proposed to compare the performance of PANI coated

chitin and PANI coated silica as corrosion resistant modifiers in epoxy with
other carbon based conducting nanofillers commercially available. Carbon
nanotubes (CNTs) and graphene are amongst the most promising nanofillers
in this regard. Very few investigations have been made on the corrosion
behaviour of CNT and graphene modified epoxy nanocoatings.
By far the most widely investigated nanofillers for epoxy based

nanocoating is nanoclays or nanosilicate materials. However not much
attention is given to halloysite nanoclay based epoxy nanocoatings. Hence it
is proposed to investigate the effect of halloysite nanoclay as corrosion
resistant modifier in epoxy.
The specific objectives of this work are
a) To study the effect of two different crosslinkers on the curing process

of a selected epoxy resin so as to develop a soft coating and a hard
coating and to study the properties of the coatings.
b) To study the effect of a commercially important conducting polymer

polyaniline (PANI) on the morphology, mechanical, thermal and
corrosion resistant properties of soft and hard epoxy coatings by
i) Converting PANI into a nanoconducting filler by coating it over

an inert organic material chitin and inorganic material silica both
at nanosize to develop PANI coated chitin nanofiller and PANI
coated silica nanofiller.

Introduction
ii) Modifying epoxy based soft and hard coatings using PANI coated
chitin and PANI coated silica.
c) To study the effect of commercially available carbon based

nanofillers, carbon nanotubes and graphene, on the morphology,
mechanical, thermal and corrosion resistant properties of soft and hard
epoxy coatings.
d) To study the effect of a clay based nanofiller, halloysite nanoclay, on

the morphology, mechanical, thermal and corrosion resistant
properties of soft and hard epoxy coatings.
e) To study the effect of zinc powder on the mechanical and corrosion

resistant properties of soft epoxy coatings.
f) To study the effect of selected hybrid fillers on the mechanical and

corrosion resistant properties of soft epoxy coatings.
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Introduction
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Introduction

1.1 Metallic corrosion

A general introduction to polymeric coatings, nanofillers, polymeric

1 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

a) Polymeric binder which controls the drying characteristics of the

1.1 Metallic corrosion

The most common type of corrosion can be considered as an

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 2

due to two half-cell reactions. In one of the half-cell reactions known as

Fig.1 Corroded Refugee ship from China. Courtesy: The Minerals,

The use of polymeric coatings is one of the most important

3 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

Alkyds, polyester-amides, polyester polyether-amides,

1.2.1 Epoxy resins

The epoxy resin belongs to the family of thermosetting polymers

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 4

coefficient of thermal expansion etc which restrict their use in more

Glycidyl Glycidyl Glycidyl

Fig.2 Types of Epoxy resins

5 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

Glycidyl ester epoxy resins are usually less viscous, highly

1.2.2 Curing agents/ crosslinkers for epoxy resins

A significant variable governing the development of a successful

Polyamide amines react with bisphenol-A type epoxy resin to cure

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 6

anionic polymerizing/curing agent for epoxy resin characterized by a

1.3 Fillers (modifiers) for improving the corrosion resistance

Fillers are solid particles used in polymeric coatings to improve

a) Properties of the coating

1.3.1 Fillers (modifiers) which influence barrier properties

The permeability of a coating refers to the ability of small

7 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

1.3.2 Conducting polymers as modifiers for improving the corrosion

Conducting polymers such as polyaniline (PANI), polypyrrole and

Conducting polymers can be coated over other substrates for

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 8

The addition of a nanofiller to an epoxy coating can be a good

Nanomaterials are a very interesting development of recent times.

9 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

1.9.3.1 Carbon based nanofillers

Carbon based nanomaterials (eg: carbon nanotubes, graphene

Fig.3 Development of electrical conductivity

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 10

The presence of uniformly dispersed nanofillers is a basic

Carbon nanotubes (CNTs) were discovered by a Japanese physicist

Fig.4 Schematic diagram of multi-walled carbon nanotube

11 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

Carbon nanotubes possess extraordinary heat and electrical

The conventional methods of preparing carbon nanotubes are arc

Graphene is pure carbon in the form of a very thin, nearly

Fig.5 Schematic diagram of graphene

Studies on Epoxy Nanocomposite Coatings for Corrosion Protection 12

Graphene is the basic structure of graphite, carbon nanotubes and

13 Studies on Epoxy Nanocomposite Coatings for Corrosion Protection

Plate like montmorillonite is the most commonly used nanoclay.

Halloysite nanoclay is a naturally occurring alumina silicate

Fig.6 Schematic diagram of halloysite nanoclay

Due to the hollow tube structure halloysite nanoclay is used for